WO2012081645A1 - Procédé pour la séparation d'une substance active à pôle positif et procédé pour la récupération de métaux de valeur de batterie lithium-ion - Google Patents

Procédé pour la séparation d'une substance active à pôle positif et procédé pour la récupération de métaux de valeur de batterie lithium-ion Download PDF

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WO2012081645A1
WO2012081645A1 PCT/JP2011/078972 JP2011078972W WO2012081645A1 WO 2012081645 A1 WO2012081645 A1 WO 2012081645A1 JP 2011078972 W JP2011078972 W JP 2011078972W WO 2012081645 A1 WO2012081645 A1 WO 2012081645A1
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Prior art keywords
positive electrode
active material
electrode active
slurry
lithium ion
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PCT/JP2011/078972
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English (en)
Japanese (ja)
Inventor
工藤　敬司
人士 石田
浅野　聡
幸恵 川上
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住友金属鉱山株式会社
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Priority to EP11848381.7A priority Critical patent/EP2653573B1/fr
Priority to US13/991,512 priority patent/US9023130B2/en
Priority to CN201180060370.9A priority patent/CN103261455B/zh
Publication of WO2012081645A1 publication Critical patent/WO2012081645A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a method for separating a positive electrode active material and a method for recovering valuable metals from a lithium ion battery to which the separation method is applied.
  • водород batteries secondary batteries having a performance corresponding to the equipment to be used are required, but in general, lithium ion batteries are mainly used.
  • This lithium ion battery includes a negative electrode material in which a negative electrode active material such as graphite is fixed to a negative electrode substrate made of copper foil in a metal outer can such as aluminum or iron, and lithium nickelate or cobalt on a positive electrode substrate made of aluminum foil.
  • a positive electrode material to which a positive electrode active material such as lithium acid is fixed, a current collector made of aluminum or copper, a separator made of a resin film such as a porous film of polypropylene, and an electrolytic solution or an electrolyte are enclosed.
  • the first chemical treatment is to peel off the positive electrode active material containing the valuable metal from the positive electrode substrate (positive electrode foil) (Al or the like).
  • an acidic solution such as an aqueous sulfuric acid solution or an alkaline solution such as sodium hydroxide has been used for the stripping treatment of the positive electrode active material.
  • the liquid used in the positive electrode active material separation step includes many substances that obstruct the subsequent recovery of valuable metals, such as electrolytes and organic substances, and requires wastewater treatment. Therefore, it is preferable not to elute valuable metals into this liquid.
  • the positive electrode active material when the positive electrode active material is separated using an acidic solution or an alkaline solution, there is a problem that the separated positive electrode active material aggregates and the separation of the positive electrode active material from the positive electrode material becomes incomplete. This is because when the added acid or alkali reacts with the positive electrode material, a part of the positive electrode material dissolves to generate hydrogen gas, and the positive electrode active material adheres around the generated gas bubbles. it is conceivable that. Furthermore, since the aggregate of the positive electrode active material easily adheres to the positive electrode material to be separated, for example, it is difficult to perform a process of mechanically separating the positive electrode active material and the positive electrode material in a subsequent process. This was a cause of a decrease in the recovery rate of the active material.
  • the separation process of the positive electrode active material in the method for recovering valuable metals from lithium ion batteries by conventional wet processing not only causes recovery loss due to elution of valuable metals, but also causes aggregation of the positive electrode active material. It could not be sufficiently separated from the positive electrode material, causing a reduction in the recovery rate of the positive electrode active material. This also causes a reduction in the recovery rate of valuable metals.
  • the present invention has been proposed in view of such circumstances, and improves the recovery rate of the positive electrode active material and prevents the recovery loss of valuable metals when separating the positive electrode active material from the lithium ion battery. It is an object of the present invention to provide a method for separating a positive electrode active material that can be used, and a method for recovering valuable metals from a lithium ion battery to which the separation method is applied.
  • the present inventors have used valuable surfactants contained in the positive electrode active material by using a surfactant when separating the positive electrode active material from the lithium ion battery. It has been found that the loss of valuable metals can be suppressed by preventing the elution of. In addition, after adding an alkaline solution to produce a slurry containing a positive electrode active material, a surfactant solution is added to the slurry, thereby preventing recovery of valuable metals and suppressing aggregation of the positive electrode active material. It has been found that the recovery rate of the positive electrode active material can be improved.
  • the present invention is a method for separating a positive electrode active material for separating a positive electrode active material constituting a lithium ion battery from a positive electrode substrate, wherein a battery disassembled product obtained by disassembling a lithium ion battery is treated with a surfactant solution.
  • the positive electrode active material is separated from the positive electrode substrate by using and stirring.
  • the present invention also relates to a method for recovering valuable metals from a lithium ion battery, in which a battery disassembly obtained by disassembling a lithium ion battery is immersed in a surfactant solution and stirred.
  • an alkaline solution is applied to the positive electrode material of the battery disassembly obtained by disassembling the lithium ion battery. Is added to dissolve the positive electrode substrate to which the positive electrode active material is fixed to obtain a slurry containing the positive electrode active material, and a surfactant solution is added to the slurry to disperse the positive electrode active material in the slurry. It is preferable to separate the active material and the alkaline solution.
  • the valuable metal contained in the positive electrode active material is eluted into the solution by performing a stirring treatment using the surfactant solution.
  • the positive electrode active material can be effectively separated with no recovery loss of valuable metals.
  • the present invention after obtaining a slurry of the positive electrode active material with an alkaline solution, a treatment using a surfactant solution is performed, thereby suppressing the aggregation of the positive electrode active material and effectively providing the positive electrode active material.
  • a treatment using a surfactant solution is performed, thereby suppressing the aggregation of the positive electrode active material and effectively providing the positive electrode active material.
  • the recovery rate of the positive electrode active material can be improved and the recovery loss of valuable metals can be prevented.
  • FIG. 1 is a diagram showing the steps of a method for recovering valuable metals from a lithium ion battery.
  • FIG. 2 is a diagram illustrating a processing step performed in the positive electrode active material separation step S3.
  • 3A is an appearance photograph of a substance having a size of 2380 ⁇ m or more after sieving in Example 5
  • FIG. 3B is an appearance photograph of a substance having a size of 2380 ⁇ m or more after sieving in Comparative Example 2.
  • the present invention is a method for separating a positive electrode active material and a method for recovering valuable metals from a lithium ion battery to which the separation method is applied, and separates a positive electrode active material constituting a lithium ion battery from a positive electrode substrate (positive electrode foil).
  • the separation is performed using a surfactant.
  • a mechanical stirring process is performed using a surfactant solution.
  • a slurry containing a positive electrode active material with an alkaline solution it is more preferable to obtain a slurry containing a positive electrode active material with an alkaline solution and then add a surfactant solution to the slurry for treatment.
  • a positive electrode material of a battery disassembly obtained by disassembling a lithium ion battery a positive electrode substrate to which the positive electrode active material is fixed using an alkaline solution is dissolved to obtain a slurry containing the positive electrode active material, A surfactant solution is added to the obtained slurry to disperse the positive electrode active material in the slurry, and the positive electrode active material and the alkaline solution are separated.
  • the surfactant is added to the slurry and then treated, so that the surfactant is a bubble of hydrogen gas. Aggregation of the positive electrode active material on the surface can be prevented, and the positive electrode active material can be dispersed in the slurry in a fine shape. Then, by separating the positive electrode active material and the alkaline solution containing the positive electrode substrate from the slurry in which the positive electrode active material is dispersed in this way, it is possible to suppress recovery loss of the valuable metal due to the elution of the valuable metal into the solution. In addition, only the positive electrode active material can be effectively separated and recovered at a high recovery rate.
  • the present embodiment a specific embodiment relating to a method for recovering a valuable metal from a lithium ion battery to which the present invention is applied (hereinafter referred to as “the present embodiment”) will be described in more detail as an example.
  • the valuable metal recovery method includes a crushing / disintegrating step S1, a cleaning step S2, a positive electrode active material separating step S3, a leaching step S4, and a sulfiding step S5. Note that the method of recovering valuable metals from the lithium ion battery is not limited to these steps, and can be changed as appropriate.
  • (1) Crushing / disintegrating step In the crushing / disintegrating step S1, in order to recover valuable metals from the used lithium ion battery, the battery is disassembled by crushing / disintegrating. At this time, since the battery is dangerous in a charged state, it is preferable to make the battery harmless by discharging the battery prior to disassembly.
  • a discharge solution such as an aqueous solution of sodium sulfate or an aqueous solution of sodium chloride is used, and the used battery is discharged by immersing it in the aqueous solution.
  • the harmless battery is disassembled into an appropriate size using a normal crusher or crusher.
  • the outer can can be cut to separate and disassemble the positive electrode material, the negative electrode material, and the like inside, but in this case, it is preferable to further cut each separated part into an appropriate size.
  • the washing step S2 the battery disassembled material obtained through the crushing / disintegrating step S1 is washed with alcohol or water to remove the electrolyte and the electrolyte.
  • the lithium ion battery includes an organic solvent such as ethylene carbonate, propylene carbonate, diethyl carbonate, and dimethyl carbonate, and an electrolyte such as lithium hexafluorophosphate (LiPF 6 ). Therefore, by removing these in advance, it is possible to prevent organic components, phosphorus (P), fluorine (F), and the like from being mixed as impurities in the leachate in the positive electrode active material separation step S3 described later.
  • the battery disintegrated material For washing the battery disassembled material, alcohol or water is used, and the battery disintegrated material is charged preferably at a rate of 10 to 300 g / l, and the organic components and the electrolyte are removed by shaking or stirring.
  • alcohol ethanol, methanol, isopropyl alcohol, and a mixture thereof are preferable.
  • Carbonates that constitute battery materials are generally insoluble in water, but ethylene carbonate is arbitrarily soluble in water, and other organic components have some solubility in water, so they can be washed with water. .
  • the amount of the battery disassembled product with respect to alcohol or water is not economical if it is less than 10 g / l, and if it exceeds 300 g / l, the battery disassembled product is bulky and difficult to clean.
  • the battery disassembled product It is preferable to repeatedly clean the battery disassembled product a plurality of times. Further, for example, it may be repeated by changing the components of the cleaning liquid, such as cleaning with only alcohol and then cleaning again with water.
  • the components of the cleaning liquid such as cleaning with only alcohol and then cleaning again with water.
  • phosphorus, fluorine and the like derived from the organic components and the electrolyte can be removed to the extent that they do not affect the subsequent steps.
  • the positive electrode active material separation step S3 the positive electrode active material fixed to the positive electrode substrate (positive electrode foil) is separated and separated from the battery disassembled material obtained through the cleaning step S2. .
  • the following processing is performed in the positive electrode active material separation step S3.
  • an alkaline solution is added to the positive electrode material of the battery disassembly obtained through the cleaning step S2 to fix the positive electrode active material.
  • a slurry generation step S31 for dissolving the positive electrode substrate and obtaining a slurry containing the positive electrode active material, and adding a surfactant solution to the generated slurry and stirring the dispersion to disperse the positive electrode active material in the slurry.
  • a separation step S32 for separating the substance and the alkaline solution containing the positive electrode substrate and the like.
  • the battery disassembled material is stirred using the surfactant solution in this manner, thereby suppressing the valuable metal in the positive electrode active material from being eluted into the solution, and the recovery loss of the valuable metal. Can be prevented.
  • a hydrophobic compound such as Teflon (registered trademark) or polyvinylidene fluoride (PVDF) as a binder is applied on an aluminum foil as a positive electrode substrate. Therefore, in the present embodiment, it is considered that the surfactant permeates from the surface or interface of the hydrophobic compound to promote peeling without dissolving the positive electrode active material or the aluminum foil. .
  • the positive electrode active material is peeled off while the positive electrode substrate is dissolved with an alkaline solution to generate a slurry containing the positive electrode active material, and then a stirring process is performed to add a surfactant to the slurry. I do.
  • the aggregate of the positive electrode active material that has been aggregated in the slurry can be dispersed in the slurry, and it can be suppressed that the aggregate is adsorbed to the positive electrode material after peeling the positive electrode active material, Further, since the difference in size from the positive electrode material becomes significant, only the positive electrode active material can be effectively separated and recovered from the slurry.
  • the concentration of the alkaline solution to be added is not particularly limited, but is preferably 0.3 to 1.0 N.
  • concentration of the alkaline solution is less than 0.3N, aluminum which is the positive electrode substrate where the positive electrode active material is not applied is dissolved, but the positive electrode substrate where the positive electrode active material is applied is sufficiently dissolved. In other words, the positive electrode active material may not be effectively peeled off even after 60 minutes.
  • concentration of the alkaline solution is higher than 1.0 N, there is a possibility that even the positive electrode active material is dissolved, and efficient treatment cannot be performed from the viewpoint of economy.
  • the battery dismantled product is a term including a material obtained by selecting only the positive electrode material portion from the battery dismantled product. Therefore, in this slurry production
  • the positive electrode material is generally thin, so an alkaline solution may be added as it is, but the positive electrode material is cut into a predetermined size in advance.
  • An alkaline solution may be added later.
  • the cutting size is not particularly limited and is preferably changed as appropriate depending on the processing conditions. For example, the length of one side is cut to a size of 30 mm square or less, preferably about 10 mm square or less.
  • the smaller cutting size is preferable, it is preferable to make it 2 mm square or more in consideration of labor and cost required for cutting, loss due to scattering of cut pieces, and influence on the environment. Thereby, it is possible to prevent the positive electrode materials from coming into close contact with each other and prevent dissolution by the alkaline solution, and efficiently recover the positive electrode active material.
  • the slurry containing the positive electrode active material obtained in the slurry generation step S31 is then sent to the separation step S32, where the positive electrode active material and the alkaline solution containing the positive electrode substrate and the like are separated.
  • the separation step S32 as described above, a surfactant solution is added to the generated slurry and subjected to a stirring treatment, and the positive electrode active material in the slurry is dispersed to contain the positive electrode active material, the positive electrode substrate, and the like. Separate from alkaline solution.
  • the positive electrode active material can be effectively separated and recovered from the positive electrode substrate without the valuable metal eluting into the solution and causing a recovery loss of the valuable metal. it can.
  • the surfactant solution added in the separation step S32 is not particularly limited, and any known surfactant solution such as a nonionic surfactant, an anionic surfactant, or a cationic surfactant should be used. They can be used alone or in combination of two or more.
  • nonionic surfactant examples include polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, and the like.
  • anionic surfactants alkyl diphenyl ether disulfonate and its salt, bisnaphthalene sulfonate and its salt, polyoxyalkylsulfosuccinate and its salt, polyoxyethylene phenyl ether sulfate and its salt Etc.
  • cationic surfactant examples include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridinium salts, imidazolium salts, and the like.
  • a nonionic surfactant solution having a polyoxyalkylene ether group in view of low foamability and low pH dependency.
  • a positive electrode active material can be disperse
  • the concentration of the surfactant solution to be added is preferably 0.1 to 10% by weight.
  • concentration preferably 0.1% by weight or more, the positive electrode active material in the slurry can be more effectively dispersed, and the positive electrode active material can be recovered with a high recovery rate.
  • concentration can be effectively separated without economical loss.
  • the separation step S32 it is preferable to add a physical treatment such as stirring and sliding to the solution obtained by adding the surfactant solution to the slurry containing the positive electrode active material.
  • a physical treatment such as stirring and sliding to the solution obtained by adding the surfactant solution to the slurry containing the positive electrode active material.
  • the treatment is performed using a well-known stirring device equipped with stirring blades.
  • the stirring speed of the stirrer may be appropriately adjusted depending on the type of surfactant solution and the amount added, and is preferably 300 to 850 rpm, for example.
  • the stirring speed is too slow, the stirring effect may not be sufficiently exhibited, and the positive electrode active material may not be effectively dispersed and separated.
  • the stirring speed is too high, it is not preferable because bubbles are easily involved, and the aluminum foil of the positive electrode substrate is sheared and becomes fine by the stirring blade, which may be mixed into the positive electrode active material. It becomes impossible to separate.
  • the stirring time by the stirring device is preferably 30 to 120 minutes.
  • the stirring time is too short, the dispersion effect of the positive electrode active material is not sufficient.
  • the stirring time is too long, the dispersion effect of the positive electrode active material does not appear any longer, and efficient treatment cannot be performed.
  • stirring when stirring using a stirring device or the like, it is preferable to use a stirring medium.
  • the stirring efficiency can be increased, and the positive electrode active material in the slurry can be more efficiently dispersed and the positive electrode active material can be separated.
  • the agitation media used for agitation are not particularly limited.
  • ceramic spheres such as silicon nitride spheres, silicon carbide, zirconia, and alumina
  • steel spheres such as chrome spheres (ball bearing steel balls) and carbon spheres (carbon steel balls).
  • chrome spheres ball bearing steel balls
  • carbon steel balls carbon steel balls
  • a stainless steel ball a sphere coated with a film of titanium nitride, titanium carbonitride, or the like.
  • the amount of the stirring medium added is preferably 100 to 200 g, particularly 170 to 200 g.
  • the stirring efficiency cannot be sufficiently increased.
  • improvement of a recovery rate cannot be aimed at but it is inefficient.
  • a slurry is obtained that dissolves the positive electrode substrate to which the positive electrode active material is fixed by adding an alkaline solution to the positive electrode material of the battery disassembled material, thereby obtaining a slurry containing the positive electrode active material.
  • a generation step S31 and a separation step S32 for adding a surfactant solution to the generated slurry to disperse the positive electrode active material in the slurry and separating the positive electrode active material and the alkaline solution containing the positive electrode substrate and the like are performed.
  • the negative electrode powder such as graphite, which is the negative electrode active material, and the accompanying substances are also included in the slurry. It is separated together with the positive electrode substrate by the process in S32, and only the positive electrode active material can be effectively recovered.
  • the leaching step S4 the positive electrode active material recovered through the positive electrode active material separation step S3 is leached with an acidic solution to form a slurry.
  • the positive electrode active material is dissolved in an acidic solution, and nickel, cobalt, etc., which are valuable metals constituting the positive electrode active material, are used as metal ions.
  • organic acids can be used in addition to mineral acids such as sulfuric acid, nitric acid and hydrochloric acid.
  • sulfuric acid solution industrially from the viewpoint of cost, work environment, and recovery of nickel, cobalt, and the like from the leachate.
  • the pH of the acidic solution to be used is preferably at least 2 or less, more preferably about 0.5 to 1.5 in consideration of reactivity. Since the pH increases as the dissolution reaction of the positive electrode active material proceeds, it is preferable to add an acid such as sulfuric acid during the reaction to maintain the pH at about 0.5 to 1.5.
  • the leaching rate of nickel or cobalt from the positive electrode active material can be improved by adding a metal or compound having a high reducing effect such as nickel metal or fixed carbon-containing material to the acidic solution.
  • a metal or compound having a high reducing effect such as nickel metal or fixed carbon-containing material
  • the fixed carbon-containing material used include graphite (fixed carbon 95% or more), activated carbon (fixed carbon 90% or more), coal (fixed carbon 30 to 95%), coke (fixed carbon 75 to 85%), charcoal. (Fixed carbon of about 85%).
  • the negative electrode powder collected by the leaching step S4 is mainly composed of graphite, it can be used, which is effective in terms of total recycling.
  • the addition amount of a metal having a high reducing effect such as nickel metal is preferably 0.5 to 2.0 times the mole of the positive electrode active material to be dissolved. Further, it is preferable to adjust by adding metal or blowing air or oxygen so that the oxidation-reduction potential (ORP) (reference electrode: silver / silver chloride electrode) is in the range of ⁇ 100 to 550 mV.
  • ORP oxidation-reduction potential
  • the amount of the fixed carbon-containing material is generally preferably about 50 to 300% by weight of the carbon amount with respect to the weight of the positive electrode active material to be dissolved. In the case of graphite or negative electrode powder having a high fixed carbon content, About 50 to 100% by weight is preferable.
  • the fixed carbon-containing material can be recovered and reused after the dissolution reaction.
  • Sulfurization step S5 the leachate obtained through the leaching step S4 is subjected to a sulfidation reaction to produce a nickel-cobalt mixed sulfide, and nickel (Ni), cobalt ( Co) is recovered.
  • the leachate obtained through the leaching step S4 may be neutralized with a neutralizing agent to separate and recover a trace amount of aluminum, copper, etc. contained in the leachate.
  • the leaching solution obtained through the leaching step S4 is introduced into a reaction vessel, and a sulfiding agent is added to cause a sulfidation reaction.
  • a sulfiding agent alkali sulfides such as sodium sulfide and sodium hydrosulfide can be used.
  • nickel ions (or cobalt ions) contained in the leachate become sulfides by a sulfidation reaction with an alkali sulfide according to the following formula (I), (II) or (III). .
  • Ni 2 + + H 2 S ⁇ NiS + 2H + ⁇ (I) Ni 2+ + NaHS ⁇ NiS + H + + Na + (II) Ni 2+ + Na 2 S ⁇ NiS + 2Na + (III)
  • the addition amount of the sulfiding agent in the sulfiding step S5 is preferably 1.0 equivalent or more with respect to the contents of nickel and cobalt in the solution.
  • the concentration of nickel and cobalt in the solution can be made 0.001 g / l or less.
  • the pH of the solution used for the sulfurization reaction in the sulfurization step S5 is preferably about pH 2 to 4. Further, the temperature of the sulfurization reaction in the sulfurization step S5 is not particularly limited, but is preferably 0 to 90 ° C, more preferably about 25 ° C.
  • nickel and cobalt contained in the positive electrode active material of the lithium ion battery can be recovered as nickel / cobalt sulfide (sulfurized starch) by the sulfurization reaction in the sulfurization step S5.
  • the method for recovering valuable metals from the lithium ion battery according to the present embodiment is not limited to the above-described steps, and can be appropriately changed as long as the gist of the present invention is not changed. .
  • the sulfiding reaction may be generated using hydrogen sulfide as a sulfiding agent. That is, in the sulfurization reaction using hydrogen sulfide, the solution obtained through the neutralization step S5 is introduced into a reaction vessel composed of a pressure vessel having pressure resistance, and sulfide containing hydrogen sulfide in the gas phase of the reaction vessel. Blowing gas is used to cause a sulfurization reaction with hydrogen sulfide in the liquid phase.
  • This sulfurization reaction using hydrogen sulfide is performed according to the following formula (IV) under a predetermined oxidation-reduction potential that depends on the hydrogen sulfide concentration in the gas phase.
  • the pressure in the reaction vessel for the sulfurization reaction of formula (IV) is not particularly limited, but is preferably 100 to 300 kPa.
  • the reaction temperature is not particularly limited, but is preferably 65 to 90 ° C.
  • the method for recovering valuable metals from the lithium ion battery according to the present invention is not limited to the method of recovering valuable metals such as nickel and cobalt as sulfides by a sulfurization reaction using alkali sulfide or hydrogen sulfide. .
  • a neutralizer is added to the mother liquor obtained through the leaching step S4 to adjust the pH to 6.5 to 10.0 to form nickel and cobalt starches. You may make it make it. Through this nickel / cobalt recovery process, nickel and cobalt contained in the lithium ion battery are recovered.
  • the neutralizing agent used here general chemicals such as soda ash, slaked lime, and sodium hydroxide can be used.
  • the method for recovering valuable metals from the lithium ion battery according to the present invention is included in the leachate of the positive electrode active material as the de-P and F steps prior to recovering the valuable metals nickel and cobalt by sulfidation reaction or the like.
  • Phosphorus (P) and fluorine (F) derived from lithium hexafluorophosphate (LiPF 6 ) or the like in the electrolyte solution may be removed.
  • At least one compound selected from the group consisting of Ca compounds, Mg compounds, Al compounds and rare earth compounds is added to the leaching solution of the positive electrode active material, and the pH of the leaching solution is 2.0 to 4.0. More preferably, the pH is adjusted to about 3.0.
  • the pH of the leaching solution is 2.0 to 4.0. More preferably, the pH is adjusted to about 3.0.
  • Examples of the Ca compound, Mg compound and Al compound to be added include hydroxides, chlorides, nitrates and sulfates.
  • As rare earth compounds Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu hydroxides, chlorides, nitrates, sulfates Etc.
  • Example 1 The discharged lithium ion battery was disassembled into a size of 1 cm square or less by a biaxial crusher. 10 g of this battery disassembled product was immersed in 300 mL of water, and the deposits on the surface that was readily soluble in water were removed and washed. Thereafter, the weight of the disassembled material and the active material adhered thereto was measured through a 40-mesh liquid filter cylinder.
  • the positive electrode active material was separated and recovered from the battery disassembled product. After the stirring treatment, it was separated into a positive electrode active material (a) and a disassembled product such as beads + foil with a sieve having an aperture of 1.8 mm.
  • a stirrer HIDON Three One Motor FBL1200, manufactured by Shinto Kagaku Co., Ltd.
  • the disassembled material such as beads + foil on the sieve is soaked in 50 ml of 8 mol / l NaOH, the aluminum foil is dissolved again with a sieve having an opening of 1.8 mm, and the remaining positive electrode active material (b) and other than beads + foil Separated into dismantled materials.
  • Recovery rate (%) active material (a) / (active material (a) + active material (b)) ⁇ 100
  • Example 1 the positive electrode active material could be separated and recovered at a high recovery rate of 89.6%. Moreover, when the solution containing the active material sieved at this time was filtered using 5C filter paper having an opening of 1 ⁇ m and the liquid was analyzed, Co, Ni and Al, which are the main valuable metals contained in the active material, were detected. It was less than the lower limit (1 mg / l). From this, it was found that the positive electrode active material could be effectively separated without eluting the valuable metal to be recovered into the solution.
  • Comparative Example 1 As Comparative Example 1, 2.67 g of the disassembled battery used in Example 1 was immersed in 210 ml of water, and stirring was continued for 60 minutes to obtain the recovery rate of the positive electrode active material. That is, the recovery rate was obtained when only the stirring treatment was performed without using the surfactant solution.
  • Example 2 Next, in the same manner as in Example 1, the influence on the recovery rate of the positive electrode active material due to the difference in the addition amount of the surfactant solution was examined. Conditions and amounts other than the addition amount of the surfactant solution were the same as in Example 1. Table 1 shows the addition amount and recovery rate of the surfactant solution.
  • Example 1 6.35 g of the battery disassembled material used in Example 1 was immersed in 127 ml of water, and after adding 0.1 wt% of the surfactant solution, stirring was continued for 60 minutes, and the recovery rate was the same as in Example 1. Asked.
  • Example 3 In the same manner as in Example 1, the influence on the recovery rate of the positive electrode active material due to the difference in the amount of added beads was examined. Conditions other than the added amount of beads and the amounts of each substance were the same as in Example 1. Table 2 shows the amount of beads added and the recovery rate.
  • the positive electrode active material could be recovered with a high recovery rate of 85% or more in any case.
  • the recovery rate was as high as 94% or more.
  • Example 4 Next, in the same manner as in Example 1, the influence of the recovery rate of the positive electrode active material due to the difference in the stirring time by the stirring device was examined.
  • the amount and amount of the surfactant were the same as in Example 1 except that 3.3% by weight of the surfactant was added and the stirring time was changed. Table 3 shows the stirring time and the recovery rate.
  • Example 5 Battery disassembled material 118.3g, which was disassembled to a size of 1cm square or less with a twin-screw crusher, was immersed in 1068mL of pure water to remove deposits on the surface that was easily soluble in water and washed. did.
  • an aqueous solution of sodium hydroxide adjusted to a concentration of 0.6 N is added to this solution, and the positive electrode active material fixed to the positive electrode substrate is dissolved by dissolving aluminum as the positive electrode substrate while stirring at a stirring speed of 400 rpm for 60 minutes. It was made to peel and the slurry containing a positive electrode active material was produced
  • Neoperex solution concentration: 0.1 wt%, which is a surfactant solution
  • a surfactant treatment was performed at a stirring speed of 300 rpm for 30 minutes.
  • the filtrate and the residue were separated using filter paper 5C. Then, the residue was sieved through respective meshes of 2380 ⁇ m, 850 ⁇ m, and 75 ⁇ m to separate and collect the positive electrode active material, which was the purpose of collection.
  • Example 2 (Comparative Example 2) Example 1 except that 108.35 g of a battery disassembled product obtained by disassembling a discharged lithium ion battery into a size of 1 cm square or less by a biaxial crusher was not subjected to the surfactant treatment with the surfactant. And processed in the same manner.
  • the filtrate and the residue are separated using the filter paper 5C, and the residues are 2380 ⁇ m, 850 ⁇ m,
  • the positive electrode active material was recovered by sieving through 75 ⁇ m meshes.
  • Table 4 shows the weight before and after peeling with the sodium hydroxide solution in Example 5 and Comparative Example 2, the weight of the positive electrode active material / foil (positive electrode substrate) / separator after peeling, and the amount of aluminum dissolved.
  • Table 5 shows the weight of the positive electrode active material, the foil (positive electrode substrate), and the separator after sieving after separation with a sodium hydroxide solution.
  • a material screened to 75 ⁇ m or more and less than 850 ⁇ m (+75 to ⁇ 850 ⁇ m) and a material screened to less than 75 ⁇ m ( ⁇ 75 ⁇ m) were regarded as positive electrode active materials.
  • FIG. 3 shows photographs of the appearance of substances having a sieve size of 2380 ⁇ m or more in Example 5 and Comparative Example 2.
  • 3A is an appearance photograph in Example 5 where the surfactant treatment was performed
  • FIG. 3B is an appearance photograph in Comparative Example 2 where the surfactant treatment was not performed.
  • Example 5 As shown in Table 4, in Example 5, which was dissolved and peeled with an alkaline solution and then treated with a surfactant solution, the weight of 75 ⁇ m or more and less than 850 ⁇ m after sieving was 18.94 g, and less than 75 ⁇ m after sieving. The weight was 40.92 g. Therefore, the weight of the positive electrode active material that could be separated was 59.86 g in total. On the other hand, in Comparative Example 2 in which only the peeling treatment with the alkali solution was performed without performing the surfactant treatment, the weight of 75 ⁇ m or more and less than 850 ⁇ m after sieving was 18.83 g, and the weight of less than 75 ⁇ m after sieving. Was 24.71 g, and the weight of the positive electrode active material thus separated was 43.54 g in total. The recovery rate of nickel and cobalt in the recovered positive electrode active material was 92.4%.
  • Example 5 in which the surfactant treatment was performed, a positive electrode active material more than 16 g more than in Comparative Example 2 could be recovered.
  • the weight of the positive electrode active material of less than 75 ⁇ m was about 1.6 times greater than that of Comparative Example 2.
  • Example 5 by adding a surfactant to the slurry obtained by peeling with an alkaline solution and treating the slurry, the positive electrode active material is dispersed in the slurry, thereby suppressing aggregation. It was found that adhesion to the substrate or the like can be suppressed and only the positive electrode active material can be effectively recovered.
  • the positive electrode active material can be recovered at a high recovery rate, and thereby, nickel and cobalt contained in the positive electrode active material, It was found that the recovery rate of valuable metals such as lithium can be improved.

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Abstract

L'objet de la présente invention réside en l'amélioration du taux de récupération d'une substance active de pôle positif et en l'évitement de perte de récupération de métal de valeur quand la substance active de pôle positif est séparée d'une batterie lithium-ion. Au moyen de la présente invention, une batterie lithium-ion est démantelée et les débris de batterie résultants sont agités dans une solution d'agents tensioactifs pour séparer une substance active de pôle positif d'un substrat de pôle positif. De plus, de préférence une solution d'alcali est ajoutée au matériau de pôle positif contenu dans les débris de batterie, le substrat de pôle positif auquel la substance active de pôle positif adhère est dissous, une suspension contenant la substance active de pôle positif est obtenue, une solution d'agents tensioactifs est ajoutée à cette suspension et la substance active de pôle positif est dispersée dans la suspension pour séparer ainsi la substance active de pôle positif et la solution d'alcali.
PCT/JP2011/078972 2010-12-14 2011-12-14 Procédé pour la séparation d'une substance active à pôle positif et procédé pour la récupération de métaux de valeur de batterie lithium-ion WO2012081645A1 (fr)

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EP11848381.7A EP2653573B1 (fr) 2010-12-14 2011-12-14 Procédé pour la séparation d'une substance active à pôle positif et procédé pour la récupération de métaux de valeur de batterie lithium-ion
US13/991,512 US9023130B2 (en) 2010-12-14 2011-12-14 Method for separating positive-pole active substance and method for recovering valuable metals from lithium ion battery
CN201180060370.9A CN103261455B (zh) 2010-12-14 2011-12-14 正极活性物质的分离方法和从锂离子电池中回收有价金属的方法

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JP6571123B2 (ja) * 2017-03-01 2019-09-04 Ｊｘ金属株式会社 リチウムイオン電池スクラップの浸出方法および、リチウムイオン電池スクラップからの金属の回収方法
US10450633B2 (en) * 2017-07-21 2019-10-22 Larry Lien Recovery of lithium from an acid solution
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